Homogeneous olefin polymerization catalyst by abstraction with lewis acids

Abstract

A process for preparing addition polymerization catalysts having a limiting charge separated structure corresponding to the formula:LMX.sup.+ XA.sup.-,wherein:L is a derivative of a substituted delocalized .pi.-bonded group imparting a constrained geometry to the metal active site and containing up to 50 nonhydrogen atoms;M is a metal of Group 4 or the Lanthanide series of the Periodic Table of the Elements;X independently each occurrence is hydride or a hydrocarbyl, silyl or germyl group having up to 20 carbon, silicon or germanium atoms; andA.sup.- is an anion of a Lewis acid, A, having relative Lewis acidity greater than or equal to that of phenylbis(perfluorophenyl)borane, said anion being compatible with the metal cation,the steps of the process comprising contacting a derivative of a Group 4 or Lanthanide metal corresponding to the formula:i LMX.sub.2,whereinL, M, and X are as previously defined,with the Lewis acid, A, under conditions to cause abstraction of X and formation of the anion XA.sup.-.

Claims

1. A process for preparing a catalyst having a limiting charge separated structure corresponding to the formula: ##STR4## wherein: Cp is a cyclopentadienyl group or a substituted derivative thereof that is.pi.-bound to M wherein each substituent is independently selected from the group consisting of C.sub.1-20 hydrocarbyl radicals, C.sub.1-20 halogenated hydrocarbyl radicals, C.sub.1-20 hydrocarbyl substituted metalloid radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements, and halogen radicals; or two or more such radicals may together with Cp form a fused ring system;

Z is a divalent moiety comprising oxygen, boron, or a member of Group 14 of the Periodic Table of the Elements;

Y is a ligand group comprising nitrogen, phosphorus, oxygen or sulfur or optionally Z and Y together form a fused ring system;

M is a metal of Group 4 or the Lanthanide series of the Periodic Table of the Elements;

X independently each occurrence is hydride or a hydrocarbyl, silyl or germyl group said X having up to 20 carbon, silicon or germanium atoms; and

A.sup.- is an anion of a Lewis acid, A, having relative Lewis acidity greater than or equal to that of phenylbis(perfluorophenyl)borane, said anion being compatible with the metal cation,

with the Lewis acid, A, under conditions to cause abstraction of X and formation of the anion XA.sup.-.

2. A process for preparing an addition polymerization catalyst having a limiting, charge separated structure of the formula: ##STR6## wherein: Cp is a cyclopentadienyl group or a substituted derivative thereof that is.pi.-bound to M wherein each substituent is independently selected from the group consisting of C.sub.1-20 hydrocarbyl radicals, C.sub.1-20 halogenated hydrocarbyl radicals, C.sub.1-20 hydrocarbyl substituted metalloid radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements, and halogen radicals; or two or more such radicals may together with Cp form a fused ring system;

Z is a divalent moiety comprising oxygen, boron, or a member of Group 14 of the Periodic Table of the Elements;

Y is a ligand group comprising nitrogen, phosphorus, oxygen or sulfur or optionally Z and Y together form a fused ring system;

M is a metal of Group 4 or the Lanthanide series of the Periodic Table of the Elements; and

X independently each occurrence is hydride or a hydrocarbyl, silyl or germyl group, said X having up to 20 carbon, silicon or germanium atoms;

with tris(pentafluorophenyl)borane under conditions to cause abstraction of X and formation of the anion,.sup.- XB(C.sub.6 F.sub.5).sub.3.

3. A process as claimed in claim 1 wherein M is a titanium or zirconium.

4. A process as claimed in claim 1, wherein the metal derivative is an amidosilanediyl- or amidoalkanediyl-compound corresponding to the formula: ##STR8## wherein: M is titanium or zirconium;

R' each occurrence is independently selected from hydrogen, silyl, alkyl, aryl and combinations thereof said R' having up to 20 carbon or silicon atoms, and optionally two or more R' groups on the cyclopentadienyl group together with the cyclopentadienyl group may form a fused ring system;

E is silicon or carbon;

m is one or two; and

X independently each occurrence is hydride, alkyl, aryl, or halogen substituted aryl said X group having up to 20 carbons.

5. A process as claimed in claim 4, wherein X is hydride or C.sub.1 -C.sub.10 hydrocarbyl.

6. A process as claimed in claim 1 wherein the Lewis acid is a boron compound lacking in halogen moieties directly attached to the boron.

7. A process as claimed in claim 6, wherein the Lewis acid is selected from the group consisting of tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(1,2,2-trifluoroethenyl)borane, phenylbis(perfluorophenyl)borane, tris(3,4,5-trifluorophenyl)aluminum, tris(perfluorophenyl)borate, 1,3,5-cyclohexanetriol borate, and 1,1,1-trimethylolethane borate.

8. A process as claimed in claim 2, wherein each X independently is hydride, alkyl or aryl of up to 10 carbon atoms; Y is NR'; and Z is (ER'.sub.2).sub.m, wherein each R' independently is hydrogen, silyl, alkyl, aryl or a combination thereof having up to 10 carbon or silicon atoms, and E is silicon or carbon; and m is 1 or 2.

9. A process as claimed in claim 8, wherein X is hydride or C.sub.1 -C.sub.10 hydrocarbyl.

10. A process as claimed in claim 2, wherein M is titanium or zirconium.